DE2734690A1 - PROCESS FOR THE PRODUCTION OF INORGANIC-ORGANIC PLASTICS - Google Patents

Description

Process for the production of inorganic-organic plastics

Inorganic-organic plastics based on polyisocyanates and aqueous alkali silicate solutions are known; see e.g. DT-OS 1 770 384, 2 227 147, 2 359 606, 2 359 607, 2 359 606, 2 359 609, 2 359 610, 2 359 611, 2 359 612, DT-AS 2 325 090 and 2 310 559.

In this way, plastics can be produced which, due to the inorganic components, are compared to purely organic Substances above all have improved fire resistance and are foamed depending on the composition and reaction conditions or unfoamed, hard or soft, brittle or flexible. Due to the great variability of the properties these inorganic-organic plastics offer a wide range of possible applications.

What these combination plastics have in common is that the organic and inorganic phases together for their production need to be mixed. This results in dispersions of the type W / 0 (water in oil) or 0 / W (oil-in-water).

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The plastics obtained from a dispersion of the W / O type are particularly interesting. They have high mechanical strengths, even when exposed to moisture, because the hardened coherent organic phase envelops the likewise hardened aqueous inorganic incoherent phase and fixed with it. Of the perfect coherent organic phase of these plastics also depends, due to the trapped amount of water, the improved fire resistance of such systems.

Attempts have been made to produce the plastics described, the reaction components in a discontinuous or continuously working mixing device in one stage or in several stages to mix with one another and the then to allow the resulting dispersion to solidify.

For example, according to DT-OS 2 359 606, the mixing of

a) an organic polyisocyanate

b) an aqueous silicate solution

c) an organic component

carried out so that initially the portions b) and c) are premixed or else a), b) and c) are mixed at the same time.

In this way, however, one often obtains products that increase with the proportion of organic components Measures can show disturbances, which in extreme cases the regulated structure of an inorganic-organic plastic

impede.

The invention is based on the object of avoiding the disadvantages described above and of inorganic-organic Plastics, even with high amounts of organic components, can be produced without any problems.

This object is achieved with the method according to the invention.

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The present invention thus relates to a process for the production of inorganic-organic plastics of high levels Strength, elasticity, heat resistance and flame retardancy, consisting of one as colloidal Xerosol present polymer-polysilicic acid gel composite material by mixing together

a) an organic polyisocyanate

b) an aqueous basic solution and / or an aqueous basic suspension with contents of inorganic solids from 20-80% by weight, preferably 30-70% by weight,

c) an organic compound containing at least one isocyanate-reactive hydrogen atom as well contains at least one nonionic-hydrophilic group, and

d) optionally catalysts and further additives and allowing the mixture thus obtained to react completely,

characterized in that the mixing is carried out in such a way that components a) and b), optionally with the addition of all or part of component d), converted to a stable primary dispersion and then component c), optionally with the addition of all or part of component d), is added to form a final dispersion.

According to the invention it is preferred that the final dispersion is before Curing begins at room temperature and has a viscosity range of 100-4000 cP and 10-50% by weight inorganic aqueous phase and 90-50 wt .-% organic phase.

The inventive method can be continuous or preferably be carried out discontinuously. After the discontinuous mode of operation, the stable one is the first Primary dispersion of polyisocyanate, aqueous basic solution or suspension and optionally other additives such as activators, emulsifiers and propellants

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prepared and then the addition of the organic compound (component c)) made. According to the continuous working method is in accordance with the discontinuous working method by a special machine arrangement in advance the Primary dispersion generated in an antechamber, mixing with the organic compound (component c)) takes place continuously in a downstream mixing head.

The discontinuous variant is recommended when using organic compounds as component c) which, for example, aqueous alkali metal silicate solutions gel spontaneously. A stable primary dispersion is preferably first prepared from polyisocyanate and, for example, aqueous alkali metal silicate, and component c) is then added.

Often desired, longer mixing times can be achieved in the discontinuous process in that the zur The activator required for curing is only added after the stable primary dispersion has been produced.

Organic compounds according to component c) which do not gel or only very slowly gel the aqueous alkali metal silicates can be used both by the continuous and by the discontinuous process.

According to the invention, a mixing of the individual Components e.g. made in the order that spatially and temporally first from components a) and b), optionally with the addition of all or part of component d), a dispersion is produced with the help of a mixing unit and to this dispersion in a spatial and temporal manner afterwards arranged mixing unit the component c),

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optionally with the addition of all or part of component d) _{f is} added.

There are various possibilities for the technical implementation of this successive mixing:

1) Two agitator mixheads are used.

2) Two mixing units are used, two of which are mounted one after the other on a driven axle Mixing elements exist, with components a) and b) [and possibly d)] at the top of the driven Axis are metered in, component c) [and possibly l on the other hand in the lower part of the axis.

3) The mixing units consist of two static mixing devices arranged one after the other, with the Components a) and b) [and possibly d)] are metered in at the first static mixer and after passing through the first Mixing section in the second static mixer with component c) and possibly d) J are mixed.

4) The first mixing unit is an agitator mixing head and a static mixer as the second mixing unit.

5) A static mixer is used as the first mixing unit and an agitator mixing head is used as the second mixing unit.

As starting components to be used according to the invention (Component a) are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those from W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, are described, for example ethylene diisocyanate, 1,4-tetramethylene-Le A 18 214 - 5 -

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diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, Cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-Isocyanto-3,3, S-trimethyl-S-isocyantomethylcyclohexane (DT-AS 1 202 785, US-PS 3 401 190), 2.4- and 2,6-hexahydrotolylene diisocyanate, as well as any Mixtures of these isomers, hexahydro-1,3- and / or 1,4-phenylene diisocyanate, Perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, Naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanate, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and e.g. in the GB-PS 874 430 and 848 671 are described, m- and p-Isocyanatophenylsulfonyl-isocyanate U.S. Patent 3,454,606, perchlorinated aryl polyisocyanates such as those described in U.S. Patent No. 3,454,606 DT-AS 1,157,601 (US Pat. No. 3,227,138), polyisocyanates containing carbodiimide groups, as described in DT-PS 1,092,007 (US-PS 3,152,162), diisocyanates as described in US-PS 3,492,330 polyisocyanates containing allophanate groups, such as those described, for example, in British patent specification 994 890, of BE-PS 761 626 and the published Dutch patent application 7,102,524, polyisocyanates containing isocyanurate groups, such as those described, for example, in US Pat 3 001 973, in DT-PS 1 022, 789, 1 222 067 and 1 027 394 as well as in DT-OS 1 929 034 and 2 004 048 polyisocyanates containing urethane groups, such as those in the Belgian patent 752 261 or in US Pat. No. 3,394,164, containing acylated urea groups Polyisocyanates according to Polyisocyanates according to DT-PS 1 23Ο 778, polyisocyanates containing biuret groups, such as are e.g.

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in DT-PS 1,101,394 (US-PS 3,124,605 and 3,201,372) and in GB-PS 889 05O, polyisocyanates prepared by telomerization reactions, as described, for example, in US Pat. No. 3,654,106, are described. Polyisocyanates containing ester groups, as mentioned, for example, in GB-PS 965 474 and 1 O72 956, in US-PS 3,567,763 and in DT-PS 1 231 688, reaction products of the above-mentioned isocyanates with acetals according to DT PS 1,072,385, polyisocyanates containing polymeric fatty acid residues according to US Pat. No. 3,455,883.

It is also possible to remove the isocyanate group-containing distillation residues obtained during the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates, to be used. Furthermore it is possible to use any mixtures of the aforementioned polyisocyanates.

The technically easily accessible polyisocyanates, for example 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and are particularly preferred subsequent phosgenation can be produced ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or polyisocyanates containing biuret groups ("modified polyisocyanates").

Particularly preferred according to the invention are polyisocyanates containing ionic groups, as described in DT-OS 2 227 147, for example sulfonated polyisocyanates (DT-OS 2 227 111, 2 359 614, 2 359 615), Car-

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polyisocyanates containing boxylate groups (German Offenlegungsschrift No. 2,359,613). Nonionic-hydrophilic polyisocyanates, as described in DT-OS 2,325,909, are also preferred according to the invention polyisocyanates containing polar groups according to DT-OS 2 3 59 608 and phenolic OH groups Polyisocyanates, as they are mentioned in DT-OS 2,359,616.

The above-mentioned, particularly preferred polyisocyanates are preferably made from polyphenyl-polymethylene-polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ('crude MDI') and from the distillation residues obtainable therefrom by distilling off two-core products, which generally have a viscosity between 50 and 50 000 P / 25 ° C, an NCO content of 28-33 percent by weight and a functionality > ■ 2, produced.

According to the invention, the starting components (component b)) Aqueous basic solutions or suspensions with an inorganic solids content of 20-80% by weight, preferably 30-70% by weight, especially aqueous alkali silicate solutions or alkaline stabilized silica sols, but also liquid-flowable basic suspensions of finely divided fillers are used. Often the aforementioned aqueous basic solutions or suspensions are also used in combination.

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Aqueous solutions of alkali silicates are to be understood as meaning the solutions of sodium and / or potassium silicate in water, usually referred to as "water glass". It is also possible to use raw technical solutions which can additionally contain, for example, calcium silicate, magnesium silicate, borates and aluminates. Preferably, however, 32-54% strength by weight sodium silicate solutions are used, with a molar ratio of Na — O / SiO ₂ of 1: 1.6 to 1: 3.3.

Component c) is to be understood as meaning organic compounds (preferably liquid at room temperature) which except have at least one isocyanate-reactive hydrogen atom at least one nonionic-hydrophilic group.

The nonionic-hydrophilic groups are primarily hydrophilic polyether groups.

Preference is given here to polyether groups which are composed of ethylene oxide and / or propylene oxide.

Suitable organic compounds which, in addition to one isocyanate-reactive hydrogen atom, have at least one nonionic-hydrophilic group, are particularly polyethers, which are expanded from alcohols with a functionality of 1-3 and ethylene oxide and / or propylene oxide and are terminal Have OH groups.

The hydrophilic center can also be created by incorporating a glycol such as tri- and tetraethylene glycol into the organic compound to be introduced.

Of course, according to the invention, they can also be produced in a different manner Having polyether or polyether groups

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Organic compounds are used if they - in addition to at least one reactive H atom - have hydrophilic groups contain, e.g. monofunctional polyethers based on monoalcohols and ethylene oxide. The ethylene oxide content in Polyether should preferably be at least 10% by weight.

Nonionic-hydrophilic compounds suitable according to the invention are also polycarbonates based on ethylene glycol, propylene glycol, tetraethylene glycol. is also an option here Formose, as described e.g. in DT-OS 2 639 084, 2 639 083, 2 714 084, 2 714 104, 2 721 186 and 2 721 093.

Furthermore, compounds are also suitable which have a hydrophilic polyester segment, e.g. triethylene glycol or diethylene glycol and contain succinic acid or oxalic acid. Such segments can in the course of the further reaction be destroyed with water glass, with hardening of the inorganic component a hydrophobization of the organic component entry.

Polyethers which are built up from amines with a functionality of 1-4 and ethylene oxide and / or propylene oxide and Terminal OH groups are also particularly suitable for the discontinuous process.

According to the invention, volatile organic compounds are optionally used Substances used as propellants. Organic blowing agents include acetone, ethyl acetate, and halogen-substituted ones Alkanes such as methylene chloride, chloroform, ethylidene chloride, Vinylidene chloride, monofluorotrichloromethane, chlorodi fluorine than, Dichlorodifluoromethane, also butane, hexane, heptane or diethyl ether in question. A blowing effect can also be achieved by adding at temperatures above room temperature with elimination of

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Gases, e.g. nitrogen, decomposing compounds, e.g. azo compounds such as azoisobutyronitrile can be achieved.

The water contained in the aqueous basic solution or suspension can also take over the function of the propellant. Furthermore, fine metal powders such as calcium, magnesium, aluminum or zinc can be produced by the evolution of hydrogen with sufficient alkaline water glass serve as a propellant, while at the same time having a hardening and strengthening effect exercise.

According to the invention, catalysts are also often used. Catalysts that can also be used are those of the type known per se, e.g. tertiary amines such as triethylamine, Tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-cocomorpholine, Ν, Ν, Ν ', N'-tetramethyl-ethylenediamine, 1,4-diazabicyclo- (2,2,2) -octane, N-methyl-N'-dimethylaminoethylpiperazine, Ν, Ν-dimethylbenzylamine, bis (N, N-diethylaminoethyl) adipate, Ν, Ν-diethylbenzylamine, bentamethyldiethylenetriamine, Ν, Ν-dimethylcyclohexylamine, Ν, Ν, Ν ', Ν'-tetramethyl-1,3-butanediamine, N, N-dimethyl-ß-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole and in particular also hexahydrotriazine derivatives.

Hydrogen atoms active towards isocyanate groups tertiary amines are e.g. triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, Ν, Ν-dimethylethanolamine and their reaction products with Alkylene oxides such as propylene oxide and / or ethylene oxide.

Silaamines with carbon-silicon bonds are also used as catalysts, as e.g. in the German patent

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document 1 229 290 are in question, e.g. 2,2,4-trimethyl-2-silamorpholine, 1, 3-diethylaminomethyl-tetrainethyldisiloxane.

Nitrogen-containing bases such as Tetraalkylammonium hydroxides, also alkali hydroxides such as sodium hydroxide, Alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate are suitable. Also hexahydrotriazines can be used as catalysts.

According to the invention, organic metal compounds, in particular organic tin compounds, can be used as catalysts.

Tin (II) salts are preferably used as organic tin compounds of carboxylic acids such as tin (II) acetate, tin (II) acetate, Tin (II) ethyl hexoate and tin (II) laurate and the dialkyl tin salts of carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, Dibutyltin maleate or dioctyltin diacetate into consideration.

Further representatives of catalysts to be used according to the invention and details about the mode of operation of the catalysts are given in the Kunststoff-Handbuch, Volume VII by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 96 to 102.

The catalysts are generally used in an amount between about 0.001 and 10% by weight, based on the amount of isocyanate, used.

Surface-active additives can also be used according to the invention

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(Emulsifiers and foam stabilizers) can also be used. The emulsifiers used are, for example, the sodium salts of castor oil sulphonates, sodium salts of sulphonated paraffins or of Fatty acids or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine in question. Even Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethanesulfonic acid or Fatty acids such as ricinoleic acid or polymeric fatty acids can also be used as surface-active additives will.

Water-soluble polyether siloxanes are primarily used as foam stabilizers in question. These compounds are generally constructed so that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane residue. Such foam stabilizers are for example in the United States patent 2,764,565.

According to the invention, reaction retarders, e.g. acidic substances such as hydrochloric acid or organic acid halides, as well as cell regulators of the kind known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments or dyes and flame retardants of the known type, e.g. tris-chloroethyl phosphate or ammonium phosphate and polyphosphate, inorganic salts of phosphoric acid, chlorinated paraffins, and also stabilizers against Aging and weather influences, plasticizers and fungistatic and bacteriostatic substances, fillers such as barium sulfate, kieselguhr, carbon black or whiting chalk can also be used.

Further examples of optionally also to be used according to the invention surface-active additives and foam stabilizers

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as well as cell regulators, reaction retarders, stabilizers, flame retardants, plasticizers, dyes and fillers as well as fungistatic and bacteriostatic substances and details of the use and The mode of action of these additives is described in the Kunststoff-Handbuch, Volume VI, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pp. 103 to 113. The reaction components are preferably mixed at room temperature.

To interpret the technical advantages according to the invention, it is assumed that the process according to the invention in the meantime produced primary dispersion is extremely stable and also other additives this stable state over the Do not jeopardize the reaction and curing times.

According to the previous state of the art, however, as a rule, dispersions are obtained which have an increasingly higher proportion of organic components go through unstable dispersion states with a change in the W / 0 phase structure, which after Curing can result in disturbances in the structure of the inorganic-organic plastic.

Because organic substances can, using conventional mixing techniques introduced, initiate separation processes and thereby the production of technically useful inorganic-organic Prevent plastics. It is believed that such additives make up the inorganic phase gel and / or that due to premature crosslinking reaction with the polyisocyanate sufficient mixing of the organic and inorganic phase is absent.

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The process products are used for organic-inorganic plastics, e.g. as sound and heat insulation materials, as building material, as concrete and joint sealing compounds.

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Examples

(Unless otherwise stated, percentages are percentages by weight).

Starting materials:

a) polyisocyanate component

A ₁ : Sufficient diisocyanatodiphenylmethane is distilled off from the crude phosgenation product of an aniline / formaldehyde condensate that the distillation residue has a viscosity of 400 cP at 25.degree. (2-core portion: 45.1% by weight, 3-core portion: 22.3% by weight, proportion of higher-core polyisocyanates: 32.6% by weight) NCO content: 30-31% by weight .

_{A: A 1} sulfonated with gaseous sulfur trioxide (sulfur content: 0.96%, NCO content: 30.5%, viscosity at 25 ° C.: 24,000 cP, preparation see DT-OS 2 227 111).

A _1: According sulfonated with chlorosulfonic acid A ₁ (sulfur content: 0.9%, NCO content: 30.2% viscosity at 20 C: 2000 cP).

b) silicate component

B-: sodium water glass, 44% solids, molar weight ratio Na ₂ O: SiO ₂ = 1: 2

B ₂ : sodium water glass, 51% solids, molar weight ratio Na ₂ O: SiO ₂ = 1: 2

B ₃ : sodium water glass, 48.6% solids, molar weight ratio Na ₂ O: SiO ₂ = 1: 2

c) polyether

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C ₁ : Polyethylene oxide monoalcohol started on n-butanol, OH number: 49.2

C ₂ : Polyethylene oxide-polypropylene oxide trial alcohol started on glycerine.
OH number: 56

C ^: Polypropylene alcohol started on sucrose / TMP / HjO / OH number: 380

C ₄ : Ethylenediamine started polypropylenetetraalcohol. OH number: 630

C ₅ : 2.5 parts by weight of C ₁ + 7.5 parts by weight of C ₄ C,: 5 parts by weight of C ₁ + 10 parts by weight of C.

d) Formose (prepared according to DT-OS 2 721 186) D ₁ : 14.5% H ₂ O; Acid number 9.7; OH number

e) suspension

Preparation of a chalk suspension

E ₁ : 240 g of a chalk (specific weight: 2.7, 90% of the particles <. 2 ^ u, Omyalite 90 from Omya GmbH) were in 80 g of water and 5 g of a 30% aqueous solution of a high molecular weight Suspended di-potassium salt of a maleic acid-styrene copolymer with carboxylate and sulfonate groups. Solids content: 75%.

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example 1

100 g polyisocyanate A 300 g silicate component

5 g
5 g

Polyether polyether

₁ ? T

in

Component I.

Component II

15 g tris (ß-chloroethyl) phosphate 0.2 g stabilizer 05-710 (poly-

ether siloxane from Bayer AG)

3 g dimethylbenzylamine 1 g amine catalyst (consisting of

75 wt .-% Ν, Ν-dimethylaminoethanol and 25 wt .-% diazobicylooctane)

25 g trichlorofluoromethane _

Component III

Components II and III were premixed. Component I was 10 sec. to achieve the primary dispersion with a high speed stirrer mixed, the mixture of components (II + III) was then within 5 sec. added with stirring. To 20 sec. Total mixing time, the reaction mixture was poured into a paper packet, started after 30 seconds. to froth up and was after 85 sec. stiffens. A viscoplastic, inorganic-organic lightweight foam was obtained a bulk density of 48 kg / m and a compressive strength of 0.07 ^ MPaJ.

Comparative example

A conventional, simultaneous mixture of the three components according to Example 1 leads to a foam which is not in line with practice, with foam defects and a defoamed, wet bottom zone.

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These segregation phenomena in the area of the soil zone
are obviously caused by insufficient mixing of the individual components.

Example 2

10Og polyisocyanate A ₁ ")

200 g silicate component B ₁ J P ^Kom ° ^{component τ}

5 g polyether C ₁ ~?

5 g polyether C ₂ J ^K ° ^m P ° nente II

15 g tris (ß-chloroethyl) phosphate

0.5 g stabilizer L 5340 (polyether siloxane from Union Carbide Corp.)

3 g dimethylbenzylamine component III

1 g of amine catalyst according to Example 25 g of trichlorofluoromethane

The foaming took place as in Example 1. The foaming process started after 28 seconds. on, after 7 5 sec. the reaction mixture was frozen.
Density ^ kg / m_7: 34
Compressive strength ßVPaJ : 0.06

In the following examples:

t_ = stirring time, mixing time of the mixture of component I,

Component II and component III t _T = idle time, period from the start of mixing to the start of foaming, setting time

Hardening.

t - setting time, period from the start of mixing to

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Example 3

Example 2 was repeated with an additional 3 g of polyether C _{3 in component II.} A light foam was obtained with the following data:

t: 20 sec., t _T : 33 sec., t .: 85 sec. KL-A

Density / Tcg / m 7: Compressive strength ^ MPa7: 0.04

Example 4

100 g of polyisocyanate A ₁

300 g of silicate _{component B 1} J component I.

5 g of Polyether C ₁ "1

5 g polyether C ₂ ^ J component II

15 g of tris (ß-chloroethyl) phosphate η

0.5 g stabilizer L 5340 according to 7 component III

Example 2 -J

3.0 g dimethylbenzylamine 1

1.0 g of amine catalyst according to Example 1 r component III 30 g of trichlorofluoromethane ^ J

The foaming took place according to Example 1. This gave

a lightweight foam with the data:

t _o : 20 sec .; t _T : 40 sec .; t .: 105 sec.

Density / itg / mV: Compressive strength / MPa /: 0.07

Example 5

100 g of polyisocyanate A ₁ 300 g of silicate component B ₃

"1 J P ° ^{Kom component}

5 g polyether 5 g polyether C ₃

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15 g tris (ß-chloroethyl) phosphate

0.5 g stabilizer L 5340 according to Example 2

1.5 g dimethylbenzylamine

1.0g amine catalyst according to Example 1

30 g trichlorofluoromethane ^

The foaming took place according to Example t _n : 20 sec .; t _T : 29 sec .; t,: 105 sec ,; Bulk density ßiq / mji 50

Component III

Compressive strength ^ MPa /: 0.09 Example 6

100 g of polyisocyanate A- ^

300 g of silicate component B- V component I. 100 g high-alumina cement "Lafargel"

Fondu "_J

5 g polyether C 7

^ i ·. ** - »- / -. (Component II 5 g polyether C_ _j *

15 g tris (ß-chloroethyl) phosphate O, 5 g stabilizer L 5340 according to Example 2

4.0 g dimethylbenzylamine

1.0 g of amine catalyst according to Example 1

30.0 g trichlorofluoromethane

• Component III

The foaming took place according to the example

t _R : 20 sec .; tj .: 42 sec .; t_: 90 sec .; Density frq / m ³ j '61
Compressive strength / KPgJ: 0.12

Example 7

100 g of polyisocyanate A ₁ component I

2OO g of silicate component B- J

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10 g polyether C ₄

j "

Component II

15g tris (ß-chloroethyl) phosphate

1 g stabilizer according to Example 2

0.5 g dimethylbenzylamine

25 g trichlorofluoromethane ^

Component III

The foaming took place according to Example 1. A tough-elastic, inorganic-organic lightweight foam is obtained with the values:
t_: 20 sec .; t _T : 34 sec .; t. : 140 sec .;

Conventional, simultaneous mixing of the 3 components leads to inhomogeneous, non-foamable Reaction mixtures.

Further inorganic-organic foams produced according to Example 7 are listed in Table 1.

It means:

TCAP: Tris (ß-chloroethyl) phosphate R ₁₁ : Trichlorofluoromethane

L 5340: polyether siloxane from Union Carbide Corp.

DB: dimethylbenzylamine

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* T a b e lie 1 I. Silicate
component (9) component II Component III DB Anin-
cataly-
sator (G) V (sec) t _A bulk density (kg / in) Compressive
speed > Type 300 ^r polyether ^ri
C 4 CAPE L534O (g) (g) 30th (sec) 27 (sec) 71 (MPa) 18 214 component ^B 3 300 (G) (G) (G) 0.5 0.2 30th 20th 20th 105 62 0.24 ^ Example Polyisocyanate B ₂ 300 10 15th 1.0 1.0 30th 20th 31 125 57 0.18 No. Type (g) ^B 1 B ₁ 300
cement 10 15th 1.0 3.0 1.0 30th 20th 31 80 72 0.09 8th A ₁ 100 10 15th 1.0 3.0 1.0 20th 80 0.11 OO 9 A ₁ 100 10 15th 1.0 O
co 10 A, 100 1886 / "J A ₁ 100
100 g Iafarge '-Ν
O ro
OJ «J
c *> example 1

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Example 12 dlo

10Og polyisocyanate A- ι

300 g silicate component B ₁ J "

10 g polyether C ₅ J component II

15 g tris (ß-chloroethyl) phosphate "Ί

1.0 g stabilizer L 5340 according to Example 2

3.0 g dimethylbenzylamine

1.0g amine catalyst according to Example 1

30.0 g trichlorofluoromethane

Component III

Components II and III were mixed. Component I was 10 sec. to achieve the primary dispersion with a high speed stirrer mixed, the mixture of components (II + III) was then within 5 sec. added with stirring. To 20 sec. Total mixing time, the reaction mixture was poured into a paper packet, began after 37 seconds. to froth up and after 40 seconds was frozen. A tough, elastic, inorganic-organic lightweight foam with a bulk density was obtained of 48 kg / m and a compressive strength of 0.09 / FlPaJ.

Further inorganic-organic foams produced according to Example 12 are listed in Table 2:

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Tabel

A ₁ 100 Silicate
component
Type (g) 1 B ₁₅₀₀ Καηρ. II 10 TCAP
(G) Component III IT Amine +)
kataly
sator
(G) «11
(G) (sec) t ^ t _A bulk density
(sec) (sec) (kg / m ³ ) 95 46 Compressive strength
(MPa) A ₁ 100 B ₃ 200 Polyether
Type (g) 10 15th L534O
(G) 0.5 - 25th 20th 28 80 34 0.11 Al 100 B ₁ 200 ^C 5 10 15th 1.0 1.0 1.0 25th 20th 32 110 58 0.07 NLJU (JUi mil JjOO g B, 300 ^C 5 10 15th 1.0 0.5 0.2 30th 20th 27 87 73 0.13 te I Al 100 B ₁ 300
Lafarge cement 15th 15th 1.0 3.0 1.0 30th 20th 40 110 80 0.14 Example polyisocyanate
No. type (g) I example 100 ^C 5 15th 1.0 3.0 1.0 40 20th 42 0.09 * -> 13th ^C 6 1.0 14th 15th 16 17th

273 ^ 690

Example 18

100 g polyisocyanate A ₁

300 g of silicate _{component B 1} 'component I

10 g polyether C ₅ 1.0 g Leguval SF38 ⁺ 1.0 g benzoyl peroxide

'Component II

1.5 g tris (ß-chloroethyl) phosphate

1.0 g stabilizer L 5340 according to Example 2

3.0 g dimethylbenzylamine

1.0g amine catalyst according to Example 1

30.0 g trichlorofluoromethune

• Component III

Components II and III were premixed. Component I was 10 sec. to achieve the primary dispersion with a high speed stirrer mixed, the mixture of components (II + III) was then within 5 sec. added with stirring. After 20 sec. Total mixing time, the reaction mixture was poured into a paper packet and began to foam after 34 seconds and was after 90 sec. stiffens. A tough, elastic, inorganic-organic lightweight foam with a bulk density was obtained of 47 kg / m and a compressive strength of 0.10

+) Unsaturated polyester resin from Bayer AG, Example 19

400 g of polyisocyanate A ₂

100 g trichlorofluoromethane f component 1

0.2 g stabilizer L 5340 according to example 2

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2 7 3 Λ R 9 O

600 g of silicate component B ₁

0.2 g emulsifier (sodium salt of a γ component II sulfochlorinated paraffin mixture C, _- C ,.)

120 g Formose D ₁ L _{component τιτ}

3 g triethylamine _J

Components I and II were 5 sec. mixed with a high-speed stirrer to achieve the primary dispersion. Component III was subsequently within 5 seconds. added with stirring. After 20 sec. Total mixing time the reaction mixture was in
a packet of paper poured out. You got a hard one
Heavy foam with the values:
t _R : 20, t _L : 30, t _ft : 53
Bulk density / Jcg / m ³ ?: 212
Compressive strength £ RPäJi 0.60

A conventional, simultaneous mixture of all three
Component leads within 20 seconds. to an inhomogeneous,
highly viscous, non-foamable reaction mixture.

Example 2 0

40OO g polyisocyanate Ά j

1 g stabilizer L 5340 according to example 2

8OO g trichlorofluoromethane

6000 g of silicate component B ₁

■ Component I

_{Component ττ} 1 g emulsifier according to Example 19 J)

1200 g Formose D ₁

Component III 27 g of triethylamine

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According to Example 19, components I + II were premixed with a high-speed stirrer, component III was then within 5 seconds. added with stirring. After 30 sec. After intensive mixing, the reaction mixture was poured into a wooden box with a volume of approx. 55 dm and began after 48 seconds. to foam up and was after 70 sec. stiffens. A hard inorganic-organic foam with a bulk density of 169 kg / m 2 and a compressive strength of 0.57 ßü? Aj was obtained

Example 21

400 g polyisocyanate A3 ~ \ 85 g trichlorofluoromethane ^ component I.

0.2 g of stabilizer L 5340 according to I Example 2 -J

600 g of silicate _{component B 1} - component II 0.2 g of emulsifier according to Example 19 ^ J

120 g Formose D ₁ Lv *. _TTT

^ 1 γ component III

3.0 g of triethylamine

The foaming took place according to Example 19, t_: 20 sec .; t _L : 30 sec .; t_: 50 sec.

Density RqZm ³ Ji 225 Compressive strength / HPa7: 0.58

Example 22

400 g polyisocyanate A 2 "")

100 g trichlorofluoromethane V component I.

0.2 g stabilizer L 5340 according to Example 2 U

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600 g silicate component B ₁ /

0.2 g emulsifier according to Example 19 Γ component II

300 g high-alumina cement "Lafarge"

Fondu " - ^

120 g of formose D ₁ C _{component ττι}

3.0 g triethylamine -J

The foaming took place according to Example 19. t _R : 20 sec .; t _L : 29 sec .; t _ft : 55 sec.

Gross density ZTcg / m ³ 7: 229
Compressive strength / MPa7: 0.42

Example 2 3

400 g of polyisocyanate A ₂ ~) 100 g of trichlorofluoromethane

0.2 g stabilizer L 5340 according to example 2

• Component I

600 g of silicate _{component B 1} J component II 0.2 g of emulsifier according to the example

19 y

120 g Formose D ₁ ~)

500 g suspension E ₁ V component III

3 g triethylamine J

The foaming took place according to Example 19. t _D : 20 sec .; t _T : 31 sec .; t,.: 65 sec .;

Gross density ßüq / mj ·. 166 Compressive strength ^ RPä7: 0.37

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Example 24

A dispersion of waterglass (50% solids content) and polyisocyanate A _{1 is} prepared in a first stirrer, which is then mixed with a mixture M of the following composition in a second stirrer:
100 wt. Tie polyether (polypropylene oxide, started on

Ethylenediamine, OHN = 450) 200 wt. Tie trichloroethyl phosphate, 300 parts by weight trichlorofluoromethane,

10 Gew.-Tie triethylamine and

10 parts by weight of silicone stabilizer (OS 710, sales product Bayer AG).

The product flows are set at the following values: water glass 8000 g / min, polyisocyanate 8040 g / min., 4920 g / min, the mixture M. Both mixing units have spiked stirrers in an approx. 300 ml mixing chamber at 3000 rpm. the Conveyance takes place via commercially available gear pumps.

A uniformly fine-celled foam with a bulk density of 14 kg / m 2 is obtained, which is continuous without difficulty can be produced in heights of up to 80 cm with a width of 100 cm.

Example 25 (comparative example)

With product streams of the same size as in Example 24 all components fed into a single mixing head at the same time. The resulting foam is clear heterogeneous and shows strong flowing surges on the ground and on the sides

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up to a height of approx. 60% of the block height reach up. The disturbances cannot be eliminated by increasing the stirrer speed up to 6000 rpm; Likewise, adding more stabilizer does not bring about any noticeable improvement, but leads too quickly shrinking foams.

Example 26

With product streams of the same size as in Example 24, a dispersion of water glass and isocyanate is first produced in a mixing unit as in Example 24, which is fed to a static mixer and mixed with the mixture M there. An equally good foam as in Example 24 is obtained.

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Claims (8)

Claims) 7 Ί /, R ^ ft 1. Process for the production of inorganic-organic plastics high strength, elasticity, heat resistance and low inflammability consisting of an as colloidal xerosol present polymer-polysilicic acid gel composite material by mixing a) an organic polyisocyanate b) an aqueous basic solution and / or an aqueous basic suspension with contents of inorganic solids from 20-80% by weight, preferably 30-70% by weight, c) an organic compound containing at least one isocyanate-reactive hydrogen atom as well contains at least one nonionic-hydrophilic group, and d) optionally catalysts and further additives and allowing the mixture thus obtained to react to completion, thereby characterized in that the mixing is carried out in such a way that initially components a) and b), optionally with the addition of all or part of component d) to a stable primary dispersion implemented and then component c), optionally with the addition of all or part of the component d), is added with the formation of a final dispersion. 2. The method according to claim 1, characterized in that the aqueous, basic solution or suspension is aqueous Alkali silicate solutions or aqueous silica sols are used. 3. The method according to claim 1 and 2, characterized in that the alkali silicate used is sodium silicate with an Na ₂ O: Si0 ₂ molar ratio in the range from 1: 1.6 to 3.3. Le A 18 214 - 32 - 809886/0473 4. The method according to claim 1-3, characterized in that phosgenation products are used as organic polyisocyanates the aniline / formaldehyde condensation can be used. 5. The method according to claim 1-4, characterized in that the polyisocyanate used is an ion group having Polyisocyanate used. 6. The method according to claim 1-5, characterized in that the polyisocyanate containing ion groups is a sulfonic acid and / or polyisocyanate containing sulfonate groups. 7. The method according to claim 1-3, characterized in that the polyisocyanate is a terminal isocyanate group nonionic prepolymer containing hydrophilic groups is used. 8. Inorganic-organic plastics obtainable according to claim 1 from 10-50 wt .-% inorganic aqueous phase and 90-50 wt .-% organic phase. Le A 1 8 2 I 4 -.JJ-